Process of catalytic kydhation of profylenes



Sept. l, 1936. w. H. sHlFl-LER ET AL PRocEss oF CATALYTIC HYDRATION oF PRoPYLENEs Original Filed Aug. 22, 1930 Inventors @www Mm 072. @ff/m90 /l/armys Ebatentec Slept i9 i193@ 13,052, 71 s ses or saremmo perron @F si NES ot @alito tion oi Deia ses Meisters. norm, s more to Stan San Erano, C., a corporal been largely through the absorption of the ole-- dns in relatively strong sulphuric acid with a consequent formation of the alkyl sulphuric acids.

rile any1 Salemme scid has then been diluted' l with the hydrolysis ci the alkyl sulphuric Vacids l5 'to alcohol.

. The alcohols have then been distilled from the dilute sulphuric acid solutions thus produced..

lfliis procedure includes several inherent disadvantaees, among.wliich are, rst, the tact that considerable quantities of the olefins are polymerized to oils by which the ultimate yield of a1- cohols is reduced; second, three separate steps are involved'in the process requiring consider-V able expense for equipment and operation, and, 2

are produced which must be concentrated for .re-use in the process.

it is the general object oi' the present invention to provide a process by which these lower olens may be hydrated into alcohols in a single operation and in which the polymerization of the olens to oil is practically eliminated, and by which the yield of alcohols is very materially increased and the cost of equipment and operation of the process materially reduced.

By the process of the present invention, we are able to produce high yields of alcohol from the lower oleinswithout substantial polymerization oi the olens to oils and without the necessity of dilution of the sulphuric acid used so that the cost incidental to re-concentratins sulphuric acid is removed.

ln the hydration of olens and alcohols by a three-step process which involves the absorption of the oleflns in acid, the dilution of the acid and distillation of the alcohols from the diluted acid, it is recognized that concentrated sulphuric acids and relatively low temperatures should be employed such, for example, as acids containing about between 95% and 100% sulphuric acid-and temperatures of from 90 F. to 200 F., depending upon the f particular olen to be absorbed. An attempt is made to secure a. complete absorption of the oleiins by the concentrated sulphuric acid in one passage of the olelns into the acid. Genthird, large quantities of dilute sulphuric aciderally considered, the .process oi the present invention embodies the use of a comparatively dilute lsulphuric acid, preferably 'containing not over sulphuric acid and temperatures sufncient to cause the volatilization of the nydrav5 tion products as theyI are formed.v The olens are passed continuously through the sulphuric acid, preferably accompanied by the addition of sumcient steam to maintain the concentration of the acid constant throughout' the process. n l0 this manner, only part of the olens are absorbed by the sulphuric acid during a single passage of the olens through the acid, this part being hydrated and volatilized without the necessity of any separate dilution oi theacid. l le By a, continuous condensation from the gas oi the hydration products produced and a continuous recirculation of the unreacted' olens back for further contact with the acid e. substantially complete hydration ci the olens may be caused 20 to take place.

In the process the sulphuric acid remains unchanged in strength and quantity, thus operating as a catalyst for the direct hydration oi the oleiins. 25

It has also been discovered that the conversion of the ethylene to ethyl ether and ethyl alcohol is an equilibrium reaction and that by main' taining in the ethylene gas passed through. the acid a correct quantity of either ether or alcohol, 30 the reaction may be caused to produce either solely etheror solely alcohol. It has also been discovered that the conversion oi propyene to Visopropyl alcohol is an eduilibriumreactlon, but vthat very little isopropyl ether is produced under 35 the conditions most favorable for the production of isopropyl alcohol.

It has been further discovered that while in .ultimate effect the process is a direct catalytic hydration of the olens, it tal-:es place apparently 40 in two steps occurring simultaneously in the process. the first step consisting of an absorption of the oleiins by the acid and the second step the distillation of the alcohols from the acid. A sufcient surface of sulphuric acid may be supplied 45 to insure adequate contact with all of the olefin gas and yet the rate of hydration oi' the olens may be so slow as to render the process commercially impractical.

When, however, a considerable body of sul- 50 phuric acid is supplied for contact with the gas a. high rate of production may be obtained.

It has been further found that the catalytic hydration oi' oleilns takes place best with acids between 20 and 80% in strength. The weaker 55 yac acids provide a lower production rate, while, on the other hand, the stronger acids have a tend fency to polymerize or osridize the olefins. It has been further found that by operating the process under a pressure which is high, the rate'oi pro"-l ouction of the process may be materially in= creased. High pressures have also a tendency to increase the ratio between the amount of ether and the amount or alcohol produced.

rEhe present invention will best be understood from a description of one or more examples oi the invention. For this purpose, we have hereafter set forth the preferred torni or forms of processes embodying the invention. The process is described in connection with the accompanying drawing, in which:

The gure is a diagrammatic view of an ap paratus suitable for conducting the process.

In the drawing, i represents a contacting chamber, in this instance a vessel preferably lined with lead and bricis. The chamber may be about two-thirds filled with suitable packing material such as stoneware Raschig rings il. The contents or the chamber may mf supplied with heat by ay suitable means, such as the closed steam coil d. Glenn gas is supplied through lines i2 and d, being distributed evenly through the chamber by means of a perforated distributing coil it. Steam from line i@ is passed into the chamber through lines d along with the 'olefin gas. Unire acted olen gas and steam mixed with alcohol and ether vapors' together with impurities or diluents carried in the gas fed, leave the chamber through linee and enter the condenser t where most of the alcohol, ether and steam are condensed. The condensed liquid is separatedv from the gas in a drum l and sent through line 9 to the storage tank The unreacted gas leaves the top of the drum 'l throughline i@ where it may be passed by means of a circulating blower 3 back to the charnber through line d and the cycle repeated. If the oleiln gas contains impurities, such as ethane and Vmethane or propane, part of the cycle of gas may be returned to a puriiication plant through line id. A pressure gauge i3 indicates the pressure in the system. The condensate is pumped from the storage tank 8 to a still, lnot shown, where y the alcohol and ether may be separated. If it isA desired to return either the alcohol or ether to chamber i, this may be done through line l5.

The process will be described as appliedv to the production ofiscpropyl alcohol from propylene. The catalyst employed is preferably sulphuric acid of a strength between 20% and 75% or 80%. The preferred operating conditions are at 55% sulphuric acid. At an acid strengthv of 46% the rate of production is only about one haii that at 55%.

The reaction proceeds more slowly the weaker the acids, acids below 20% producing a negligible quantity o1 alcohol, while stronger acids, especially at high temperatures, tend to polymerize Aand oxidize the propylene and so reduce the yield of alcohol.

lThere are several ways in which the catalyst may be contacted with propylene gas, but it is important that not only a large reactive surface of the catalyst and propylene be obtained but' that there be an ample volume o sulphuric acid in the process. One method of contacting the gas with the acid is to fill the chamber about twothirds full of sulphurlc acid and bubble the gas through the acid. Preferably, the .chamber also contains sized acid-proof screenings or small stoneware Raschig rings which are immersed in atrasos 'step process, andunless there is a large body of acid present a low reaction rate will be obtained, even when all or the gas is thoroughly contacted with the acid. Preferably, the acid is maintained at a temperature of between 200 and 270 F., or above or about preferably 240V F. At a tempera ture of 210 F. the production rate is only about two-thirds that oi 2e@ li.

The entire process is preierably maintained under a pressure above atmospheric. it a pres= sure or thirty pounds per square inch above at mospheric production is about two and a half times that at atmospheric pressure. in addition, the strength of isopropyl alcohol produced is increased about two and a haii times. The propyl= ene gas may be pure propylene gas, ii the same is obtainable, but we prefer to employ a gas pros duced by fractionation of the gases obtained from the hydrocarbon cracking processes. Simul taneously with the introduction of propylene, we introduce sumcient steam or water into the catalyst to compensate for the water lost from the `acid during the process and thus maintain the acid throughout the process at' a constant strength. it is desirable to'introduce water or steam continuously or simultaneously with the propylene, but since .there is a wide range of acid strengths over which the process is satis y the strength of acid in the chamber may beanalyzed from time to time by withdrawing sa= ples of the acid through the line il.

There issues trom the suiphuric acid catalyst mixed vapors oi isopropyl alcohol and unconverted propylene and diluent gases, if such diluent gases exist in the gas being processed. 'The streamer gases and vapors passes out of the chamber to the condenser and the vapors con dense so that alcohol and ether are collected. The gases, after separation of the alcohol and ether, may be returned to the process for further conversion.

Under the operating conditions that we have found most suitable for the process, only about 14% of propylene is converted to alcohol during the single passage oi the propylene through the catalyst. -It is important that the alcohol and ether be condensed from Athe vapors leaving the chamber before the unreacted gas is recycled Yor again contacted with the acid, as apparenti/pout little further conversion of propylene into alcohol can taire place while the valcohol produced re mains with the propylene gas.

By condensing the alcohol from the propylene gas and returning the same to the system with sumcient make-up gas to maintain a constant pressure on the system, the process is rendered continuous and a high yield of hydration products may be obtained from the propylene. Impuritiesin the gas, such as methane, ethane, and the like, are prevented from building up in the system by a release of part of the gas to be recycled or by returning a. part or all of the *gas to a puriiication plant through the line M. In the purification plant the gas may be fractionated to concentrate its propylene content and lthen the gas may be returned to the process.

The rate of release of such gasv for purication may be determined by the alcohol strength desired in the condenser and by the amount` of lmpurities in the make-up gas, and this may be conveniently done by analyzing the gas in the system at intervals and maintaining the olen content constant. As the impurities build up in the system, the partial pressure of the propylene is reduced and the ratio of water to alcohol in the condenser increases. The isopropyl alcohol collected in the storage tank is separated by distillation.

When the propylene gas is rst passed through fresh acid in the chamber, a considerable period of time generally elapses before the alcohol production reaches its maximum. Thus, several hours time usually passes before the alcohol production arrives at a maximum value. The alcohol production apparently does not reach a maximum until sumcient propylene has been absorbed and retained by the acid to reach a certain maximum formation of alkyl sulphuric acid. The production of alcohol is dependent upon the decomposition of the alkyl sulphuric acid and a high rate of production is dependent upon having a large volume of acid present in which this decomposition reaction may be taking place.

In general, with propylene it will be seen that the process may be satisfactorily operated with stronger or weaker acids than those specified in the examples given above and with pressures higher or lower than those specified. With the weaker acids, higher temperatures and/or higher pressures should be employed for obtaining eiiicient results.

While the process herein described is well adapted for carrying out the various objects and advantages of the present invention. it is to be understood that we do not wish to be limited to tion and removal of such isopropyl alcohol from the acid along with the unreacted propylene, removing from the unreacted propylene a part at least of such isopropyl alcohol, recycling the propylene for further contact with suiphuric acid,

and adding water or steam to the acid sufficient to compensate for that vaporlzed by the gas, the sulphuric acid being maintained in substantially uniform concentration during contact with the propylene.

2. A process of manufacturing isopropyl alcohol from propylene, which consists in bringing a propylene containing gas into intimate contact with the body of sulphuric acid catalyst at a strength and at a temperature above about 240 F. suiicient to cause a minor percentage only of the propylene to be absorbed-by the acid in one passage and to cause 'simultaneously the absorbed propylene to be finally converted into isopropyl alcohol which is vaporized from the acid and passes of with the unreacted propylene, such absorption taking place at a pressure above atmospheric, condensing a part at least of the isopropyl alcohol from the-unreacted propylene, and recycling the unreacted propylene for further contact with the catalyst, the sulphuric acid being maintained in substantially uniform concentration during contact with the propylene.

3. A process of manufacturing isopropyl alcohol from propylene, which comprises continuously passing propylene into contact with a substantial body of sulphuric acid at a temperature- .and concentration of acid suiiicient to cause hydration of a minor percentage only of the propylene and volatilization of the isopropyl alcohol formed from the propylene along with the unconverted propylene gas, continuously condensing the isopropyl alcohol from the propylene gas and continuously recycling the gas again into contact with sulphuric acid while supplying sufficient fresh propylene containing gas to maintain a substantially constant pressure above atmospheric throughout the process.

4. A process ofmanufacturing isopropyl alcohol from propylene. which comprises continuously passing propylene into contact with sulphuric acid at a temperature and concentration ot acid sufficient to cause hydration of a minor percentage only of the propylene and volatilization of isopropyl alcohol along with the unconverted propylene gas, continuously condensing hydration products from the propylene gas and continuously recycling the gas again into contact with the sulphuric acid while supplying sumcient fresh gas to maintain a substantially constant pressure above atmospheric throughout the process, the sulphuric acid being maintained between 20 and 80% ln strength by the passage of sufficient water vapor providing material as to compensate for the vaporization of water from the acid during the process.x

WILLIAlVI H. SHIF'FLER.

MELVIN M. HOT M. 

